Anthraquinone compounds

ABSTRACT

Water-soluble anthraquinone dyes which bear one or two 3,5,5trimethylcyclohexylamino groups in the 1- and/or 4-positions and one or two -SO3H groups bound either directly to a carbon atom of an aromatic ring or indirectly over an oxygen atom to a carbon atom of an aliphatic chain.

C United States Patent 1 [111 3,882,150 Fre ct al. Ma 6, 1975 ANTHRAQUINONE COMPOUNDS [75] Inventors: Woligang Frey, Munchenstein [56] References cued Basel-Land; Wolfgang Schoenauer, UNITED S A S PATENTS Riehen/BS, both of Switzerland 2,117,569 5/1938 Peter 260/380 [73] Assi nee: Sanrloz Ltd., Basel, Switzerland FOREIGN PATENTS OR APPLICATIQNS g [22 Fil d N 17 1971 255,968 2/1949 Switzerland 260/37] 541,637 1 1932 Germany 260/380 [2]] Appl. No.: 199,810

Related U s Applicafion Data Primary ExaminerLorraine A. Weinberger 62 f Assistant ExaminerPatrick J. Hagan 1 g z g gf 808322 March 1969 Attorney, Agent, or FirmGerald D. Sharkin; Richard E. Vila; Thomas C. Doyle [30] Foreign Application Priority Data 57] ABSTRACT i82 Water-soluble anthraquinone dyes which bear one or Sept 6 1968 Switzerland i "1693/68 two 3,5,S-trimethylcyclohexylamino groups in the 1- and/or 4-positions and one or two SO H groups [52] U S Cl 260/380 260/371 260/37} bound either directly to a carbon atom of an aromatic 260/378 260/381 ring or indirectly over an oxygen atom to a carbon 51 Im. Cl. cove 97/14 3mm aiphafic chain- [58] Field of Search 260/380, 373 6 Claims, No Drawings ANTHRAQUINONE COMPOUNDS R for hydrogen or lower alkyl. This isadivision ofapplication Ser. No. 808,322 filed R for hydrogen, lower alkyl or alkoxy, halogen or Mar. 18, i969, now US. Pat. No. 3,646,071. lower acylamino,

This invention relates to new anthrac quinone corn- ROM CHPCHPCHF. CHE VCH*V pounds, the processes of their production and their uses. These anthraquinone compounds are of formula CH3 --CH3G}ICHI, CHCH1- 01 CH(CHg- CH3 OH 2H5 CH3 on, on; A1NH H 10 Rmfor -CHQ, CIZHCH;(JJ, -(]3II-CH1-CH1 C 3 CH3 (1) CH; AH;

CHCHICH1, where A. represents one of the radicals l5 CH1 0 NH2 0 NH2 Hz CH ll on,

so 11 R R1 3 1 R for hydrogen or alkyl having I to 8 carbon atoms. R1 R1 R12 for CH2, Q!

| ll 0 O CII, (II) (III) ClH:

o IVE-Ra NH-R X for -O or S. ll alkylene for CH CH -CH I B 01 Hots- -CH- CH;-(|3II- or z-. H e m OH: on,

5 0 W (V) m for l or 2,

n for l to 3, p for l to 9 and r for l to 6. The SO H group in formula (V) may be in the 6- or 7-position; the nucleus B may bear a chlorine atom or an SO H group in the 6- or 7-position or two hydroxyl ln formulae (ll) to (V) one R, stands for a hydrogen, fluorine, chlorine or bromine atom or a -SO H group and the other R, for a hydrogen atom, or R, in each instance stands for a chlorine atom,

or amino groups or one hydroxyl and one amino group R f r :2 Rq-U-SO H or (CH,).,, Z in the 5- and 8-positions, respectively; the nucleus C SOH $03K may bear 1 to 3 lower alkyl or alkoxy groups; ifn stands (Rs) for 2 every SUbStitUe-HI u may have a separate significance. R f0ralkylene-CO-1f The preferred compounds are those of formulae R S0311 S 03 NH O NH? R, for secondary alkyl having 3 to 6 carbon atoms, cy- 0 H 6 H CH= on:

v1 on:

clohexyl, 3,5,S-trimethylcyclohexyl, or (VII) (in,

ah and O (i? NH-Ra R for hydrogen, alkyl or alkoxy having 1 to 9 carbon CH3 atoms or halogen, I l

R, for CH CH CH --CH H 2 (VIII) Clh c Particularly valuable compounds of formulae (VII) l I l and (VIII) are those in which CH3 CH3 OH 0R stands for the radical of a sulphonated phenol which may bear an alkyl group in the para-position or for a sulphated 2-hydroxyethyl, 2- or hydroxypropyl, 3-hydroxypropyl or 2,3-dihydroxy- -CH.,-CH2-(OCH2-CH2),,. P w radical.

3 4 R for a sulphonated benzene radical which may bear Hal 1 to 3 lower alkyl groups, a lower alkoxy or acyl- H amino group, or for a sulphonated benzyl or phenylalkyl radical, the radical in which is coni B CH nected to the amino group through a secondary 5 1 a carbon atom, or for a radical of formula i H CH: H3 (XII) a E A SO H with 1 mole of an amine of formula R, NH and, if

the radical R contains noSO H group, treating the product with sulphur trioxide or with an agent yielding sulphur trioxide.

A second variation of the process consists in reacting 1 mole of an anthraquinone compound of formula where m stands for l or 2,

R for hydrogen, methyl or ethyl and R, for hydrogen, methyl, ethyl, chlorine, methoxy, ethoxy or acetylamino. O NH2 The new compounds are produced by reacting 1 mole of 3,5,5-trimethylcyclohexylamine with 1 mole of an anthraquinone compound of formula LB/ f NH: p NH-Ris ll L H 2 CH3 Y on, (XIII) d Hal 0 Hal with a compound of formula (IX) (X) O1 lfin p NH-Ri n Ha1R -OH, IOaS\; Ha1CHill 01' 0 Hal x1) 11o-om and treating the product with sulphur trioxide or an agent yielding sulphur trioxide; or reacting 1 mole of the aforesaid compound with 1 mole of an alkylenecar- (RQWRFOHrRWQII-{LK C boxylic acid which has 3 or 4 carbon atoms and a double bond in the a-position or with a hologenoacetic acid or with a functional derivative of these acids, and

l -Rn then reacting with an amine or formula where Hal stands for chlorine, bromine or fluorine, Y for bromine or -SO H,

R for SOaH sum in the presence of an inorganic acid halogenide and treating the product with sulphur trioxide or an agent yielding sulphur trioxide.

( A process for the production of anthraquinone com- If Y represents bromine, the reaction product is F treated with a water soluble neutral sulphite, or if R bears no -SO H group, with sulphur trioxide or an agent yielding sulphur trioxide.

A variation of the process consists in reacting l mole of an anthraquinone compound of formula (Xv) consists in reacting 1 mole of l.4-dihydroxyanthraquinone-fi-or -7-sulphonic acid with l mole of 3,5,5- trimethylcyclohexylamine and 1 mole of an amine of formula R -NH or reacting 1 mole of a compound of formula (Xll) in which the nucleus B bears a sulphonic acid group with 1 mole of an amine R NH A process for the production of anthraquinone compounds of formula Bl CH3 ii i O NH H CH: CH:

consists in reacting 1 mole of an anthraquinone compound of formula (lX) with l mole of 3,5,5-trimethylcyclohexylamine and reacting the product with 1 mole of a compound of formula and treating with sulphur trioxide or an agent yielding sulphur trioxide.

Examples of suitable compounds of formula (lX) are l-amino-2,4-dibromoanthraquinone, l-amino-4- bromo-, l-amino-4,6- and -4,7-dibromo, l-amino-4- bromo-o-chloroand -7-chloro, l-amino-4-bromo-6- and 7-fluoro-, l-amino-4-bromo-6,7- dichloroanthraquinone-Z-sulphonic acid, 1-amino-4- bromoanthraquinone-2,6- and-2,7-disulphonic acid.

The following are examples of suitable compounds of formula (X): l-phenylamino-4-bromoand -4- chloroanthraquinone, -4,6(7)-di-chloro-, -4-bromo-6- and -7-chloroanthraquinone, -4-chloro-5,8-diamino-, -5,8-dihydroxy-, -5-amino-8-hydroxyor -5-hydroxy- S-aminoanthraquinone and -4-bromoanthraquinone-6- and -7-sulphonic acid and their derivatives, which bear in the phenyl nucleus alkyl or alkoxy radicals having I to 5 carbon atoms (methyl, ethyl, isopropyl, n-propyl, n-butyl, n-amyl, tert. butyl, isobutyl, methoxy, ethoxy, n-butoxy, dimethyl, trimethyl, methylethyl, methylmethoxy, dimethoxy, diethoxy, diethyl), halogen atoms (chlorine, bromine, fluorine) or lower acylamino radicals, (acetylamino, propionylamino, n-butyrylamino, methoxycarbonylamino, ethoxycarbonylamino), as well as the corresponding compounds which are sulphonated in the substituted or unsubstituted phenyl radical; l-(2'-hydroxyethylamino)-,l-(3'- hydroxypropyl-Z '-amino 1-( 2',3 '-dihydroxypropylamino)-, l-(4'-hydroxybutyl-3'-amino)-,l l-(4'- hydroxybutyl-2'-amino)-4-chloroand -4- bromoanthraquinone, -4,6(7)-dichloro-,-4-bromo-6- and -7-chloro-anthraquinone,-4-chloro-5,8-diamino-, -5,8-dihydroxy-, -5-amino-8-hydroxy-, -5-hydroxy-8- aminoanthraquinone, -4-chloroand 4-bromoanthraquinone-- or -7 sulph0nic acid and the corresponding compounds which are sulphated on the hydroxyalkyl group; l-benzylamino-, l-(4'-phenyl-4'- methyLpentyl-Z -amino l-(4'phenyl-butyl-2 amino)- and l-(6'-phenyl-2-methyl-hexyl-4'-amino)-4-chloroand -4-bromo-anthraquinone, -4.6- or -4,7-dichloroor -4- bromo-6- or -7-chloro-anthraquinone, -4-chloro-5,8- diamino-, -5,8-dihydroxy-, -5-amino-8-hydroxy-, -5- hydroxy-S-amino-anthraquinone, -4-chloroor -4-bromoanthraquinone-6- or -7 -sulphonic acid; 1- (2'-benzyl-cyclohexylamino)-, l-(2'-B-phenylethylcyclohexylamino)-, l-[2'-(2"- or 4"-methylbenzyl)- and -ethylbenzyland -n-propylbenzyl)-cyclohexylamino]-, l-[2'-(2-4"- or -(2",6"- dimethyl-benzyl)- and -diethylbenzyl)- cyclohexylamino]-,

l-[2'-(2,4",6"-trimethylbenzyl)-cyclohexylamino1-, l-[2'-(2"- and -4"-methoxy-benzyl)- or -ethoxybenzyl)- or -n-propoxybenzyl)-cyclohexyl-amino]-, H2- (2 ,4 -dimethoxybenzyl or -diethoxybenzyl cyclohexyl-amino]-, l-(2-benzyl-4'-methyl- -4'-ethyl- -4'-tert.butyl-, -4'-tert.amyl and -4'-isooctylcylohexylamino)-4-chloroor -4-bromanthraquinone, -4 6- and -4,7-dichloroand -4-bromo-6-or -7-chloroanthraquinone, -4-chloro-5,8-diamino-, -S,8- dihydroxy-, -5-amino-8-hydroxy-, -5-hydroxy-8-aminoanthraquinone and -4-chloroor -4-bromoanthraquinone-6- and -7-sulphonic acid; as well as the corresponding compounds which are sulfonated in the aryl nucleus; 1 2'-phenylaminocarbonylethylamino l-(2-phenylaminocarbonylpropylamino l-( l phenylaminocarbonylpropyl-Z -amino lphenylaminocarbonylmethylamino-, l-(2'N-methyl- N-phenylaminocarbonylethylamino l-( 2 '-N-ethyl- N-phenylaminocarbonylethylamino)-, l-N-methyl-N- phenylaminocarbonylmethylamino-, l-N-ethyl-N- methyl, methyl-ethyl, methylmethoxy, dimethoxy, die-- thoxy, diethyl), halogen atoms (chlorine, bromine, fluorine) or lower acylamino radicals (acetylamino, propionylamino, n-butyrylamino, methoxycarbonylamino, ethoxycarbonylamino), and the corresponding compounds which are sulphonated in the substituted or unsubstituted phenyl nucleus The compounds of formula (X) can be produced by reacting 1 mole of a compound of formula N m @Q with 1 mole of an amine Rug'NHg or by halogenation of a compound of formula (XVII) (XVIII) The compounds of formula (X), in which R represents a radical of formula can be obtained by reacting l mole of a compound of formula (XVII) with 1 mole of an aminocarboxylic acid H N-alkylene-COOH and reacting with an amine of formula (XIV) in the presence of an inorganic acid halogenide or alternatively reacting with an amine of formula (XIV) with subsequent sulphonation. Another mode ofoperatlon consists in reacting 1 mole ofa compound of formula ll 0 Hal with l mole of an alkylenecarboxylic acid which has 3 or 4 carbon atoms and a double bond in the a-position, or with l mole ofa halogenoacetic acid or a functional derivative of one of these acids, after which the product is reacted with an amine of formula (XIV) in the pres ence of an inorganic acid halogenide or reacted with an amine of formula (XIV) and sulphonated.

Examples of suitable compounds of formula (XI) are l-isopropyl-, l-sec. butyl-, l-sec. amyl-, l-sec. hexyI-, l-cycIohexylamino-and l-(3',5,5'-trimethylcyclohexyIamino)-4-chloroor -4-bromanthraquinone-6- or -7- sulphonic acid. They can be prepared by reacting 1 mole of I,4-dihalogenoanthraquinone-o-or -7- sulphonic acid with 1 mole of an amine R -NH or by halogenation, preferably bromination, of a l-R -NH- anthraquinone-oor -7-sulphonic acid.

The reaction of the 3,5,5-trimethylcyclohexylamine with the compounds of formulae (IX), (X) or (Xi) can be effected at temperatures ranging from 40 to 220C. The water soluble anthraquinone compounds are best reacted in an aqueous or aqueous-organic medium, e.g., at temperatures of 45 to 100C or preferably 45 to 85C for the compounds of formula (IX) in which Y stands for SO H while the water insoluble anthraquinone compounds are best reacted in organic medium, e.g., at 80 to 200C or preferably I00 to 150C, more particularly I I0 130C, for the compounds of for mula (IX) where Y stands for a bromine atom. Mixtures of water and one or more solvents which are at least partially water soluble and are indifferent to the reactants are employed as aqueous-organic media, e.g., lower alcohols (methanol, ethanol, isopropanol, butanol, ethylene glycol), ethers (dioxan, 1,2-dimethoxyor I,2-diethoxyethane), ether alcohols (2-methoxy or 2- ethoxyethanol, 2-(2' -methoxyethoxy)- or 2-(2'-ethoxyethoxy)-ethanol), ketones (methylethyl ketone), amides (dimethylformamide, dimethylacetamide), sulphoxides and sulphones (dimethylsulphoxide, sulphola' n-tetramethylenesulphone). These solvents are used in (XIX) amounts of up to 25 or preferably 5 to 15 on the total weight ofthe mixture. (the pH value ofa saturated aqueous solution of 3,5,S-trimethylcyclohexylamine) and of a catalyst; for this purpose preference is given to alkali metal hydroxides (sodium or potassium hydroxide) and to copper catalysts (copper powder, copper-I-oxide copper-l-chloride, copper-II-oxide). To accelerate the reaction it is desirable to employ an excess of 3,5,5-trimethylcyclohexylarnine, e.g., 1.3 to 3 moles or preferably 1.5 to 2 moles, per mole of the halogenanthraquinone compound.

For the reaction in organic medium the 3,5,5- trimethylcyclohexylamine itself is employed as solvent or a solvent is used which is indifferent to the 3,5,5- trimethylcyclohexylamine and of high boiling point, e.g., 130 to 220 C, for example monoor di chlorobenzene, dimethylformamide, dimethylacetamide, dimethylsulphoxide, glycol ethers and in particular nitrobenzene. Examples of suitable acid binding agents are an excess of the amine, a tertiary amine of low volatility and of higher basicity than 3,5,5- trimethylcyclohexylamine, a basic metal salt such as sodium or potassium carbonate, or an alkali metal hydroxide. If necessary the aforenamed copper catalysts are employed.

The final products are isolated in the normal way, e.g., by evaporation, preferably at reduced pressure, water vapour distillation, or dilution with a suitable agent, e.g., with water when water soluble solvents are used, or with a lower alcohol such as methanol, ethanol or isopropanol or a hydrocarbon such as petroleum ether or ligroin. On isolation they are filtered with suction, washed if necessary and dried.

After condensation of the 3,5,5-trimethylcyclohexylamine with a compound of formula (IX) in which Y stands for a bromine atom the reaction product is reacted with a neutral, water soluble sulphite in aqueousorganic, e.g., aqueous-alcholic or aqueous-phenolic (phenol itself, a cresol or cresol mixture) medium, in which the concentrated sulphite solution forms the aqueous phase, at to 150C, preferably C, under pressure.

If the compounds of formula (X) in which R represents an aralkyl radical or a oyclohexyl radical are aeylated phonic acid chlorides (methane-and ethanesulphonic acid chlorides), arenesulphonic acid chlorides (benzene or 4-methylbenzenesulphonic acid chlorides), chlorocarbonic acid alkyl esters (chlorocarbonic acid methyl or ethyl esters) and in particular lower carboxylic acid chlorides and anhydrides (propionic acid chloride and anhydride or preferably acetic acid chloride or anhydride). The acetyl compound can be formed by adding the anthraquinone compound to five to times its amount of acetic anhydride containing 2-5 zinc chloride on the weight of the anthraquinone compound, raising the mixture from 60 to about 135l40C or preferably 80l00C and holding it at this temperature until the starting compound has disappeared, on which the mixture is cooled, run into water, the excess acetic anhydride carefully saponified and the precipitated product suctioned off, washed with water, dried and if necessary recrystallized in lOO acetic acid or in an alcohol.

After condensation with the 3,5,5-trimethylcyclohexylamine the acyl group is split off, e.g., by treatment in 55-80 or preferably 60-65 sulphuric acid at 50-80C or preferably 60-70C.

The reaction of the anthraquinone compounds of formula (Xll) with an amine R NH can be accomplished under the aforestated reaction conditions. Here again prior acylation of the trimethylcyclohexylamino group accelerates the rate of reaction, given a substantial excess of the unsulphonated amine.

If the reaction is conducted in an organic medium an alkali metal acetate, carbonate or hydroxide can be employed for an aromatic amine, depending on the strength of the amine, or an alkali metal carbonate or hydroxide for an amine of different type.

If the anthraquinone compound (Xll) bears an SO H group in the 6- or 7-position it is advisable to react in aqueous or aqueous-organic medium in the presence of an acid-binding agent, e.g., an alkaline metal acetate, bicarbonate, carbonate or hydroxide when an aromatic amine is employed, or an alkali metal hydroxide in the case of an aromatic-aliphatic amine.

Suitable amines R, NH include aminobenzene, l-amino-2-, -3- or -4-methyl-, -ethylor -isopropylbenzene, l-amino-2,4-, -2,5-or -2,6-dimethylor -diethylbenzene, l-amino-2,4,6- or -2,4,5-trimethylbenzene, l-amino-2-methyl-4,6-diethylbenzene, l-amino-4-nbutyl-, 4-isobutyl-, -4-tert-butyl-, -4-tert-amyl-, -4-namyl-, -4-isooctyl-, -4-tert-octylbenzene, l-amino-2-, -3- or -4- chloroor -bromobenzene, l-amino-2,4- dichlorobenzene, l-amino-2-, -3- or -4-methoxyor -ethoxybenzene, l-amino-2,4dimethoxyor -diethoxybenzene, 1-amino-2,5-dimethoxyor -diethoxybenzene, l-amino-2-methoxy-5-methylbenzene, l-amino- 4-acetylamino-, -propionylamino-, -butylrylamino-, -methoxycarbonylaminoor -ethoxycarbonylaminobenzene, or the monosulphonic acids of these aminobenzenes corresponding to the formulae sln aln SOQH Z-hydroxy-ethylamine,

10 phenylbutane, 4-amino-2-methyl-6-phenylhexane or their monosulphonic acids corresponding to the formulae SOsH 2-benzylor 2-phenylethyl-cyclohexylamine, 2-(2'- methylor -ethylbenzyl)-cyclohexylamine, 244'- methyl-, -ethyl or -n-propylbenzyl) -cyclohexylamine, 2-(2',4- or 2-(2',6'-dimethylor -diethylbenzyl) -cyclohexylamine, 2-(2',4',6-trimethylbenzyl) cyclohexylamine, 2-(2'- or 2-(4'-methoxy-, -ethoxyor -n-propoxybenzyl )-cyclohexylamine, 2-( 2 ,4'- dimethoxyor -diethoxybenzyl)-cyclohexylamine. 2- benzyl-4-methyl-cyclohexylamine or their sulphonic acids corresponding to the formulae s) 11 HzN alkyIene-C O-ITTO R1 and n HzN-a1ky1ene-C0N it, s 0 III The reaction of the anthraquinone compounds of formula (Xlll) with a compound can be conducted in a substantial excess of the halogen compound or in a polar solvent such as dimethylformamide, dimethylsulphoxide or preferably nitrobenzene at 90 to 200C, preferably l30l 80C or more particularly l35-l50C for the aryl halides, preferably 80-l30C or in particular l1 10C for the benzyl halides, and 80-l30C for the hydroxyalkylhalides, and in the presence of an acid-binding agent such as alkali metal acetate, carbonate, bicarbonate or hydroxide and of a copper catalyst (copper powder, copper-loxide or copper-l-chloride).

The compounds of formula (XllI) can be produced by condensation of bromamic acid or its derivatives with 3,5,S-trimethylcyclohexylamine and desulphonation, or by reaction of 1 mole ofa dihalogen compound of formula (XVII) in either sequence with 1 mole of 3,- 5,5-trimethylcyclohexylamine and 1 mole of ammonia or of an aliphatic or aromatic sulphonic acid amide (CH;,-SO NH C H ,SO -NH in the latter case with subsequent cleavage of the sulphonic acid radicals.

Amongst the halogen compounds suitable for reaction with aminoanthraquinone compounds of formula (XIII) may be mentioned bromobenzene, 1,2-, 1,3- and 1,4-dibromobenzene, l-bromo-2-, -3- and -4-methyland -ethylbenzene, l-bromo-2-, -3- and -4- chlorobenzene, l-bromo'2,-3- and -4-methoxyor -ethoxybenzene, l-bromo-2,4,6-trimethylbenzene, 1- bromo-Z-methoxy-S-methylbenzene, l-bromo-4- isopropyl-, -4-n-butyl-, 4-tert-butylbenzene, l-bromo- 4-acetylamino-, -4-propionylaminoand -4- butyrylaminobenzene, corresponding to the formula Rs) 11 Hal Z-chloroor 2-bromethanol, 2-chloroor 2 bromopropanol-l, l-chloro or l-bromo-2-propanoi, 3-chloroor 3-bromopropanol, l-chloroor l-bromo- 2,3-propanediol, corresponding to the formula HalR- -OH; benzyl chloride or benzyl bromide corresponding to the formula Hal-(EH10.

It is of advantage to react the aminoanthraquinone compounds of formula (Xlll) with benzyl alcohol in a substantial excess ofthe alcohol within the temperature range of 80 to 130C or preferably l00l C and in the presence of iodine as catalyst, the amount of iodine being about 3 to 15 or preferably 8-12 ofthe aminoanthraquinone compound The reaction of aminoanthraquinone compounds of formula (XIII) with alkylenecarboxylic acids having 3 or 4 carbon atoms and a double bond in a-position, or with functional derivatives of these acids, e.g., acrylic acid, acrylic acid ester, amide, or nitrile, methacrylic acid, methacrylic acid ester or crotonic acid, can be conveniently effected in sulphuric acid solution using sulphuric acid preferably of to 96 7c strength LII The reaction takes place at temperatures between 40 and 100C or preferably at C. The amount of alkylenecarboxylic acid employed must be at least l mole. It is often of advantage to employ an excess of the alkylenecarboxylic acid in order to achieve good yields. The addition of a further acid, e.g., concentrated phosphoric acid, can accelerate the reaction. In the course of the reaction the functional derivatives are often hydrolysed to the free acids. Should this not be so, hydrolysis is carried out subsequent to the reaction.

The reaction products can be isolated as described in British Pat. No. 841,927.

The reaction of aminoanthraquinone compounds of formula (XIII) with a halogenoacetic acid can be accomplished in melted bromacetic or chloracetic acid, if desired in the presence of an alkali metal acetate and a copper compound, at temperatures of 60 to C or optimally at 8090C, or in an inert organic solvent such as phenol, a cresol or cresol mixture or naphtha in the presence of an alkali metal acetate and a copper compound at temperatures of 100 to C or preferably l00-l20C. To isolate the product it is best to distill off the solvent, e.g., with water vapour or under reduced pressure; the product is then precipitated by the addition of salt or acid, filtered off with suction and purifled in the normal manner.

For amidation the dry carboxylic acids thus obtained are reacted with an amine of formula (XIV) in the presence of a halide of an acid (thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus pentabromide, or preferably phosphorus trichloride or tribromide) and in an inert organic solvent, e.g., a halogenated or unhalogenated hydrocarbon such as chloroform, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, or in an ether such as dioxane,l,2-dimethoxyor 1,2-diethoxyethane, diisopropyl di-n-propylether, or in a tertiary amine (pyridine, a mixture of pyridine bases, quinoline, dimethylaminobenzene or diethylaminobenzene). In place of an inert organic solvent the amine of formula (XIV) itself can be employed as solvent. The reaction is ef fected at temperatures between 0 and 50C in the presence of one of the aforenamed acid halides and is broughtto a close at temperatures of 0 to 100C or preferably 40 to 80C. The resulting carboxylic acid phenylarnides can be isolated in the normal way as described in the examples of British Pat. No. 1,061,424.

The reaction of l,4-dihydroxyanthraquinone-6- sulphonic acid with 1 mole of 3,5,5-trimethylcyclohexylamine and 1 mole of an amine R,NH, can be car ried out at temperatures of 50 to 150C or preferably at 80l20C. By the addition of boron compounds (boric acid, boron trifluoride) and/or by employing the l,4-dihydroxyanthraquinone-6-su|phonic acid wholly or partially in the form of the leuco compound, the introduction ofa second 3,5,5-trimethylcyclohexylamino group can be appreciably accelerated. The reaction can be effected in a substantial excess of 3,5,5- trimethylcyclohexylamine or, particularly when condensation with two different amines is involved, in an inert organic solvent, e.g., an alcohol such as ethanol, n-propanol, nor isobutanol, nor iso-amyl alcohol, a glycol such as ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, or tripropylene glycol, an ether alcohol such as 2-methoxy-, 2-ethoxyor Z-n-butoxyethanol, 2-(2-methoxy-, -ethoxyor -n butoxyethoxy)-ethanol, or in an ether such as dioxane, and if necessary with the addition of up to 30 water. After the condensation reaction, which takes place preferably in the absence of air, e.g., in a nitrogen or illuminating gas atmosphere, the leuco compound is reoxidized, e.g., by the introduction of air.

The reaction product of formula prepared from 3,5,5-trimethylcyclohexylamine and a compound of formula (IX), is reacted with hydroxy or thiol compounds of formulae at temperatures of e.g., 50 to 200C, preferably at 50 to 150C or optimally at 60 to 120C in the case of the thiol compounds, and 100 to 200C or more particularly 110 to 180C in the case of the hydroxyl compounds, and in the presence of acid-binding agents such as alkali metal carbonates or hydroxides. It is advantageous to react in an inert solvent, e.g., an alcohol such as ethanol, butanol, cyclohexanol, an ether alcohol such as 2-methoxy-, Z-ethoxyor 2-butoxyethanol, 2-(2'-methoxy-, 2-(2'-ethoxyor 2-(2'-butoxy-ethoxy)- ethanol, an ether such as dioxane, or in a hydrocrbon such as cyclohexane, toluene or chlorobenzene, or if the compounds of formula (IX) bear a sulphonic acid group in water in the case of thiol compounds. An excess of the thiol compound may be employed as sol vent. Suitable solvents for the reaction with hydroxy compounds include pyridine, a mixture of pyridine bases, quinoline, nitrobenzene, 2,6-di-tert. butyl-4- methylphenol, or a excess of the hydroxy compound itself. Any water present or formed prior to or during the reaction is eliminated. For the reaction of the bromine atom in the 2-position it may be of advantage to add a copper catalyst, e.g., copper-l-chloride, especially in the case of thiol compounds. The reaction products are precipitated in the known way, e.g., by dilution with a lower alcohol or, if water-solu ble or alkalisoluble hydroxyl or thiol compounds have been employed, with water or with alkali hydroxide solutions, and then filtered off with suction, washed and dried.

The treatment with sulfphur trioxide (in gaseous form diluted with air or as an adduct on pyrifine or dioxane, or with chlorosulphonic acid can be carried out in an inert solvent such as chloroform, 1,2- dichloroethane or nitrobenzene at temperatures of to 50C or preferably at l5-30C. Normally however concentrated sulphuric acid of about 96-100 strength is employed, or oleum with an 50;, content of up to about for reaction at the aforestated temperatures. Under these conditions the benzene nuclei are sulphonated and the aliphatic hydroxyl groups sulphated. For sulphation concentrated sulphuric acid can be employed at 10-20C, whilst for sulphonation at the same temperature it is advisable to employ oleum with an S0 content of 5-10 For converting the hydroxyalkyl groups into sulphatoalkyl groups aminosulphonic acid can also be employed with advantage. e.g., at l00-150C. The sulphonated or sulphated compound can be isolated by running the solutions into 5 water or into a salt solution, with the further addition of salt if necessary.

The final compounds are water-soluble dyes containing at least one SO l-l group and are employed for the exhaustion dyeing, pad dyeing and printing of wool. silk, hair fibres, polyamide and polyurethane fibres and leather. The dyeings and prints obtained on these material are of brilliant shade and have good to very good wet fastness properties (washing, milling, perspiration, water, sea water), with good rubbing and dry cleaning fastness. On polyamide fibres the light fastness is very good and better than on wool.

1n the Examples the parts and percentages are by weight and the temperatures in degrees centrigrade.

EXAMPLE 1 A mixture of 400 parts of water, 40.4 parts of sodium l-amino-4-bromanthraquinone-Z-sulphonate, 20 parts of l-amino-3,5,S-trimethylcyclohexane, 15 parts of 30 sodium hydroxide solution, 50 parts of ethanol and 1 part of copper powder is stirred for 5 hours at 65. The blue dye formed is isolated and dried in the normal way. It is of formula (VI). From aqueous solution it gives dyeings of brilliant redish blue shade on polyamide fibres which have very good wet fastness properties and outstandingly good light fastness.

This new dye has far better wet fastness properties on synthetic polyamide fibres than the known commercial dye which bears an unsubstituted cyclohexylamino group in the 4-position.

The same dye can obtained by the following alternative route. A mixture of 38.1 parts of l-amino-2,4- dibromanthraquinone, 160 parts of 3,5,5trimethylcyclohexylamine, 25 parts of anhydrous potassium ace tate and 0.5 part of copper-l-chloride is maintained at ll0-l20 until the starting material has disappeared. The mixture is then diluted with methanol and allowed to cool to room temperature. The precipitate is filtered off, washed successively with methanol and water and dried. It may be recrystallized if desired, after which 10 parts are mixed with 50 part of phenol and 20 parts of 50 potassium sulphite solution in an autoclave and reacted at 130 for l6 hours. The phenol is distilled off with water vapour and the dye salted out, filtered off with suction and washed with salt solution. If necessary it is then dissolved in hot water, filtered while hot to free it from water insoluble impurities and salted out, on which it is dried.

DY EING EXAMPLE A solution of2 parts of the dye of Example I in 6000 parts of water at 40 is prepared and to it is added 4 parts of ammonium sulphate. parts of a nylon 66 yarn are entered into the dyebath, which is then brought to the boil in 30 minutes and held at this temperature for 1 hour. Subsequently the yarn is rinsed and dried. It is dyed in a fast, brilliant reddish blue shade.

The following Table I details further dyes of formula c) IyHt CH:

NH- CH R1 SO3I1 11 Q a (j y R (.H

w l 5 din W? l l ll'l CH5 CH3 (XXI) which are specified by the substituents R present in the [O (X 6 and 7 positions and by the shade of the dyeings on W001 or synthetic polyamide lbms and its melting point (subsequent to recrystallization TABLE 1 from toluene and ethyl alcohol) is at l83l84. This [5 water insoluble dye can be sulphonated in the benzene Exampl i I Shade of dyeings nucleus by the normal methods, e.g. by treatment with Posmo posmo" 7 five times its amount of 10 oleum at 5l0. Sulpho- 3 Cl H reddish blue nation yields a blue water soluble dye which gives dye- 3 H g g ings of attractive blue shade on wool and synthetic 2 2' H 3: polyamide fibres having excellent light and wet fastness 5 -SO .,H H blue properties. 7 C1 C1 reddish blue By employing in place of bromobenzene the equiva- EXAMPLE 8 lent amount of 4-ethoxy-l-bromobenzene a dye base with melting point 19ll92 is obtained. The sulpho- 46'4.parts Of.the sodium of the f fi z nated derivative of this gives brilliant greenish blue E dlssolved m 600 parse 23 dyeings on synthetic polyamide fibres which have exdmon of pans of 1 h y roxl 6 so P cellent light and very good wet fastness properties P 1 hour l pans of f h ggf if: (washing, milling, perspiration, water, sea water), tomm a er our at e 30 gether with very good rubbing and dry cleaning fast- Phonanon f fzomplem h water'msolubli ness. This dye is of greater brilliance and is faster to Compound filtered m r s washing and perspiration than the analogous dye bearof neutral reaction and dried. It IS a dark v10 et pow er ing a cyclohexylamino group which on recrystallization from toluene melts at Z04205- When other bromobenzenes are employed, the relt has the formula sults are as follows:

Table 2 Example Bromobenzene Melting point Shade of aqueous soo. of dye base lution of the sulphonated derivative 9 1-bromo-4-me- 174 175 blue thylbenzene l0 |-bromo-2,4-di- I78 179 reddish blue methylbenzene l-bromo-2,4,6- I76 |77 do.

trimethylbenzene NH? EXAMPLE 12 A solution of 8 parts of iodine in 150 parts of benzyl alcohol is prepared at and while the temperature is being raised to 72.4 parts of l-amino-4-(3,5,5'- trimeth 1c clohexylamino)-anthra uinone are added.

H Y y q NH CH The mixture is stirred for 6 hours at 100, cooled to 80 CH: 3 (XXII) and diluted with 300 parts of isopropyl alcohol. The re- 55 sultingl-benzylamino-4-(3,5',5'-trimethylcyclohex- A mixture of 36.2 parts of the 1 amino-4-(3',S',5',- trimethylcyclohexamino)-anthraquinone thus prepared, 75 parts of bromobenzene, 15 parts of anhydrous sodium carbonate and 2 parts of cuprous chloride is reacted at 140 for 4 hours. On cooling to 100 the mixture is diluted with parts of ethyl alcohol, causing precipitation of the blue dye formed. This is filtered off, washed with ethyl alcohol and water and dried. It has the structure:

ylamino)-anthraquinone settles out and is filtered off, washed with isopropyl alcohol and then with water and dried at 100. It has the formula 45.2 parts of this dye base are dissolved in 135 parts of 100 sulphuric acid and 80 parts of 25 oleum at -8. The sulphonation reaction rums its course in 6 hours, following which the mixture is run into a mixture of 150 parts of water, 400 parts of 28 aqueous sodium chloride solution and 250 parts of ice. The dye settles out. It is filtered off, washed with 10 sodium chloride solution and dried at 100. The dye thus formed dyes synthetic polyamide fibres in brilliant blue shades which are fast to light and wet treatments.

The dyeings are faster to wet tests than comparable dyeings of the dye containing an unsubstituted cyclohexylamino group.

EXAMPLE 13 72.4 parts of 1-amino-4-(3',5',5'-trimethylcyclohexylamino)-anthraquinone are dissolved in 160 parts of benzyl chloride at room temperature, and after the addition of 18 parts of sodium bicarbonate the temperature is increased to 100. The condensation reaction takes 10 hours. After this time the mixture is cooled to 60 and the dye base precipitated with 300 parts of isopropyl alcohol. On sulphonation a dye identical with that of Example 12 is obtained.

EXAMPLE 14 36.2 parts of l-amino-4 (3',5',5-trimethylcyclohexylamino)-anthraquinone are dissolved at 70 in a mixture of 90 parts of 55% sulphuric acid and 14 parts of acrylic acid, and the solution is stirred for a further 4 hours at this temperature. It is then run into 500 parts of water at 60. The crystalline precipitate is filtered off and washed with hot water until the waste water runs virtually colourless and is of almost neutral reaction, on which it is dried at 100.

43.4 parts of l-(2'-carboxyethylamino)-4- (3",5,5"-trimethylcyclohexylamino)-anthraquinone are dissolved in 150 parts of aniline at room tempera ture. 14 parts of phosphorus trichloride are dropped in at 40. Subsequently the temperature of the reaction mixture is increased to 60 and it is held at 60-65 for 4 hours, after which time 160 parts of methyl alcohol are added which causes the dye base to settle out in crystalline form. It is filtered off, washed with methyl alcohol and then with water and dried at 100. The blue crystalline product is of formula I 1 1lH H 2 (XXV) The acrylic acid employed in this example can be replaced by the equivalent amount of 2-methylacrylic acid, in which case it is preferable to carry out the reaction in 96% sulphuric acid at -l00 in the presence of 3-5% of 100% phosphoric acid.

EXAMPLE 15 A mixture of 23.1 parts of l-(4'-methyl-4- phenylpentyl-2'-amino)-4-bromoanthraquinone. 0.] part of copper powder and 42 parts of 3,5,5-trimethylcyclohexylamine is reacted at 80-85 for 48 hours with stirring. On cooling to 60 parts of methanol are added dropwise. The precipitate formed is filtered off at 2025. washed with methanol and dried. It is of formula 10 parts of this dye base are dissolved in 40 parts of 100% sulphuric acid at 25 and the solution is stirred until no further starting material is present. It is then discharged onto ice and the precipitate thus formed is filtered off, washed with 10% sodium chloride solution and dried. A blue powder is obtained which dyes wool and synthetic polyamide fibres in brilliant greenish blue shades which have good light and wet fastness properties.

EXAMPLE 16 42.7 parts of l-(3',3,5-trirnethylcyclohexylamino)- anthraquinone6-sulphonic acid are dissolved at 2025 in 220 parts of 100% sulphuric acid, with the addition of 16 parts of bromine. The temperature is slowly increased to 75 and this temperature held for about 16 hours. On cooling the reaction mixture is run onto 650 parts of ice. The precipitated l-(3',3,5'- trimethylcyclohexylamino)-4-bromathraquinone-6- sulphonic acid is filtered off, washed with water until of neutral reaction and dried.

25.3 parts of this compound are suspended in 300 parts of water, on which 15 parts of 30% sodium hydroxide solution, 1 part of copper-l-chloride, 20 parts of isopropyl alcohol and 15 parts of 3.5,5-trimethylcyclohexylamine are added. The mixture is maintained at 6570 until the starting compound has disappeared. 1t is then run into a mixture of 100 parts of water and 15 parts of 30% hydrochloric acid to form a suspension. This is raised to 80 and the reaction product is filtered at this temperature and washed with acidified water. It is then suspended in 500 parts of water, the suspension raised to 80 and neutralised with sodium carbonate, then the final dye is salted out and isolated.

The 15 parts of 3,5,5-trimethylcyclohexylamine can be replaced by 10 parts of cyclohexylamine or 6 parts of isopropylamine, in which case the reaction can be effected without isopropyl alcohol. The dyes thus obtained give brilliant dyeings of good light and wet fastness on synthetic polyamide fibres.

An aromatic amine, e.g., 9 parts of aminobenezene or 14 parts of l-amino-4-acetylaminobenzene, can be employed for the condensation reaction, in which case 9 parts of sodium carbonate are ussed as acid-binding agent and the isopropyl alcohol omitted. The resulting dyes give brilliant blue shades of high light and wet fastness on synthetic polyamide fibres.

This same condensation reaction can be carried out with 18 parts of sodium l-aminobenzene-3-sulphonate to give a wool dye,

The l-(3,5,5'-trimethylcyclohexylamino)- anthraquinoneo-sulphonic acid employed in the foregoing as starting product is prepared as follows.

A mixture of 108 parts of sodium anthraquinone-l .6- disulphonate, 50 parts of 3,5,5-trimethylcyclohexyla mine. 40 parts of sodium 3-nitrobenzenesulphonate and 1.5 parts of copper sulphate in 360 parts of water is reacted in an autoclave for 36 hours at 160. On cooling the sodium salt of the l-(3,5',5'- trimethylcyclohexylamino)-anthraquinone-6-sulphonic acid is salted out, filtered off with suction and washed with sodium chloride solution until the filtrate runs colourless. The filter residue is dissolved in 3600 parts of water at 70, the solution acidified with hydrochloric acid (red to Congo paper) and the product then filtered off, washed with acidified water until the waste water runs colourless, and dried. The l-(3',5',5'- trimethylcyclohexylamino)-anthraquinone-6-sulphonic acid is obtained in the form of red crystals.

EXAMPLE 17 173.5 Parts (0.5 mole) of 1-(3,5',5'-trimethylcyclohexylamino)-anthraquinone are brominated in the 4-position by the method given in Example 16. 42.7 Parts of the resulting l-( 3 ,5 '5 trimethylcyclohexylamino)-4-bromanthraquinone are entered into 250 parts of acetic anhydride. After the addition of 2 parts of anhydrous zinc chloride the mixture is raised to 90l00 and held at this temperature until the starting compound has disappeared. On cooling the mixture is poured slowly into l.000 parts of water with vigorous stirring.

The temperature is kept below 30 by external cooling and stirring is continued until the acetic anhydride is completely saponified to acetic acid. At this point the precipitated product is filtered off with suction, washed with water and dried.

235 Parts of the l-(N-acetyl-N-3',5',5' trimethylcyclohexylamino)-4-bromanthraquinone thus obtained are added to l9 parts of l-phenyl-3- aminobutane and the mixture is reacted for 20 hours at l l with stirring. It is then run into a mixture of 200 parts of ice, 170 parts of water and 30 parts of 30% bydrochloric acid. The precipitated resinous compound is separated and entered in portions into l75 parts of 65% sulphuric acid. The hydrolyzing mixture is maintained at 60-70 until the red acyl compound is no longer indicated, on which it is run onto ice. The blue dye base can be recrystallized in nbutanol if desired and is then sulphonated with -l0% oleum at 30. The dye thus obtained gives blue dyeings of good light and wet fastness on synthetic polyamide fibres.

The l(3,5',5'-trimethylcyclohexylamino)- anthraquinone can be prepared as follows. A mixture of 242.5 parts (1 mole) of l-chloranthraquinone and 1,000 parts of 3,5,5-trimethylcyclohexylamine is reacted at l00 until no further l-chloranthraquinone is sulphonic indicated. The excess amine is driven off with water vapour and the residue introduced into 1,000 parts of water with the addition of sufficient concentrated hydrochloric acid to render the solution strongly acid. After stirring at 80 the product is filtered off with suction, washed with water until neutral and dried.

EXAMPLE l8 A mixture of 2l.4 parts of l-(3',5',5- trimethylcyclohexylaminQJ-4-bromanthraquinone, 20 parts of l-phenyl-3-aminobutane, 5 parts of anhydrous potassium acetate, 01 part of copper-l-chloride, 0.l part of water and 3 parts of 2-ethoxyethanol is reacted at l l0 for 48 hours with stirring. After the addition of 60 parts of n-butanol the mixture is allowed to cool. The dye base is then filtered off with suction, washed with butanol and then methanol, recrystallized in nbutanol and dried. The sulphonated product is identical with the dye of Example 17.

The l-(3',5',5'-trimethylcyclohexylamino)-4 bromanthraquinone can be replaced by l-(3',5',5'- trimethylcyclohexylamino )-4-chloranthraquinone, prepared by chlorination of l-(3,5,5'-trimethylcyclohexylamino)-anthraquinone with sulphuryl chloride in nitrobenzene with which the same dye is obtained.

EXAMPLE 1) l0 parts of l-cyclohexylamino-4- bromanthraquinone-6-sulphonic acid are entered into a mixture of 200 parts of water, 20 parts of ethyl alcohol, 20 parts of 3,5,5-trimethylcyclohexylamine, 0.5 part of copper bronze and 7 parts of 30% sodium hydroxide solution. The reaction mixture is maintained at 60-70 until no further starting material is present. The resulting compound is worked up as described in Example 16 to give a dye which is isomeric to the dye referred to in the third paragraph of Example 16 and have very similar properties to it.

The use of l-phenylamino-4-bromanthraquinone-6- in place of l-cyclohexylamino-4- bromanthraquinone-6-sulphonic acid results in a similar dye.

EXAMPLE 20 A mixture of 23.5 parts of l-(N-acetyl-N-3',5',5- trimethylcyclohexylamino)-4-bromanthraquinone, 0.01 part of copper-l-oxide, 5 parts of potassium acetate, 17.8 parts of Z-amino-l-butanol and 50 parts of n-butanol is reacted for 24 hours at 1 15C with stirring. After the addition of parts of methanol at 60 the temperature is allowed to fall to 20-25. The product settles out and is filtered off, washed with methanol and dried. 20 Parts of the product are dissolved in 100 parts of sulphuric acid and the solution is stirred at 60 for 8 hours, after which it is discharged onto ice. The precipitated dye base is filtered off, washed neutral with water and dried at 60. l0 Parts of this dye base are sulphated in 40 parts of sulphuric acid at room temperature. Subsequently the mixture is run onto ice and the precipitate filtered off, washed with l0% sodium chloride solution and dried. A powder is obtained which dyes wool and synthetic polyamide fibres in brilliant blue shades having good light and wet fastness properties.

EXAMPLE 2l The procedure of Example 20 is followed, employing in place of Z-amino-l-butanol 37 parts of 2-benzylcyclohexylamine and sulphonating the resulting dye base with 5-10% oleum. The product is a blue dye which gives dyeings of good light and wet fastness on synthetic polyamide fibres.

EXAMPLE 22 45 parts of l(2-phenylaminocarbonyl-ethylamino)- 4-bromanthraquinone are added to a mixture of 150 parts of 3,5,5-trimethylcyclohexylamine, 7 parts of anhydrous sodium carbonate and 0.5 part of copper-loxide and reacted at l30-l 35 until no further starting material is indicated. The dye base formed is isolated in the normal way and sulphonated with 7 times its amount of 3% oleum at l820 to yield a dye which is identical with that of Example 14.

EXAMPLE 23 33.4 parts of l,4-dihydroxy-S-hydroxyethylamino-S- chloranthraquinone and 20 parts of anhydrous sodium carbonate are added to 100 parts of nitrobenzene and the temperature raised to 150". Over the following hour 150 parts of 3,5,5-trimethylcyclohexylamine are added, the temperature being kept constant at 150-l55 until no further starting material is indicated. Methanol is added to the reaction mixture at 60, on which it is cooled to and the product filtered off with suction, washed with methanol and water and dried. On sulphation in accordance with the procedure of Example 20, the product dyes wool and synthetic polyamide fibres in blue green shades of good light and wet fastness.

EXAMPLE 24 When the l,4-dihydroxy-S-hydroxyethylamino-8- chloranthraquinone employed in the preceding Example is replaced by l,4-dihydroxy--( 4'- methylphenylamino)-8-chloranthraquinone and sulphonation is carried out in 5% oleum at 2025, a dye giving blue-green dyeings is obtained.

The same dye can be arrived at by reacting 30 parts of l,4-dihydroxy-5,8-dichloranthraquinone with 25 parts of 3,5,5-trimethylcyclohexylamine in 240 parts of nitrobenzene at l50 until the starting products are no longer indicated. The reaction mixture is then treated in the normal way and 12 parts of the isolated l,4- dihydroxy-5-( 3 ',5',S-trimethylcyclohexylamino )-8- chloranthraquinone are reacted with 6 parts of anhydrous sodium acetate and 75 parts of 4-methyl-laminobenzene at l70l75. On completion of the reaction the dye base is sulphonated.

EXAMPLE 25 A mixture of 10 parts of l ,4- dihydroxyanthraquinone-6-sulph0nic acid, 40 parts of 3,5,S-trimethylcyclohexylamine, 70 parts of 95% ethano], 0.8 part of zinc dust and 1,] parts of 100% acetic acid is reacted at 80 under a nitrogen atmosphere until after about 4 to 6 hours no further starting material is indicated. A jet of air is then directed through the mixture to reoxidize the proportion of dye which is still in the leuco form. The dye is then isolated and purified by the normal method. it is of blue colour and gives dyeings of bright blue shade on wool and synthetic polyamide fibres which have very good light and wet fastness. Instead of forming the leuco compound of the L4- dihydroxyanthraquinone-6-sulphonic acid in the reaction mixture, one can start from the pure leuco-1,4- dihydroxyanthraquinone-6-sulphonic acid or from a mixture of 1,4-dihydroxyanthraquinone-o-sulphonic acid and its leuco compound.

In place of ethanol another alcohol, e.g., npropanol or n-butanol, or an alcohol-water mixture, e.g., 80 parts of secondary butanol and 20 parts of water, can be employed with equally good success.

EXAMPLE 26 A solution of5.5 parts of potassium hydroxide in 200 parts of glycerol is prepared at l00-l l0 with vigorous stirring, and 23.2 parts of sodium l-amino-4-(3',5',5- trimethylcyclohexylamino)-anthraquinone-2- sulphonate and l2 parts of sodium 3-nitrobenzene-lsulphonate are added to it. The solution is reacted for 8 hours at ]20l25 with stirring, after which it is run into 800 parts of water and acidified with hydrochloric acid. The product settles out and is filtered off, washed with water until of neutral reaction and dried.

l0 parts of the resulting dye base are stirred in 40 parts of l00% sulphuric acid at l5-20 until a sample is completely soluble in water, on which the dye is isolated in the usual way. Its dyeings on wool and synthetic polyamide fibres are of brilliant violet shade and have good light and wet fastness.

The 23.2 parts of sodium l-amino-4-(3,5',5" trimethylcyclohexylamino)-anthraquinone-2- sulphonate can be replaced by 28.3 parts of the analogous 2,6-disulphonate, in which case a violet dye for wool is obtained.

EXAMPLE 27 At -l l0 7.5 parts of potassium hydroxide are dissolved in 100 parts of phenol, after which 18 parts of sodium l-amino-4-(3,5',5- trimethylcyclohexylamino)-anthraquinone-2- sulphonate are added. The temperature is increased to l7O and this temperature maintained until a sample is insoluble in water. The mixture is then allowed to cool to 100, parts of methanol are added and it is allowed to cool further to 20. The dye base is filtered off with suction, washed with methanol and then with water and dried. 10 parts of the dye base are entered into 45 parts of 5-10% oleum and stirred at 1525 until fully water soluble. The sulphonated dye is worked up in the normal way. On wool and synthetic polyamide fibres it gives dyeings of brilliant violet shade having good light and wet fastness.

The same dye can be obtained by reacting 16 parts of 1-amino-2-bromo-4-( 3 ',5 ',5 -trimethylcyclohexylamino)-anthraquinone in a mixture of lo parts of phenol, 50 parts of nitrobenzene and 7.5 parts of potassium hydroxide at 150 until the starting products have disappeared, and continuing as stated in the foregoing.

EXAMPLE 28 A mixture of 23.2 parts of sodium l-amino-4- (3',5 ',5 '-trimethylcyclohexylamino )-anthraquinone-2- sulphonate, l3.5 parts of 30% sodium hydroxide solution, 100 parts of water and 22 parts of 4-methyl-l-mercaptobenzene is reacted for 24 hours at 95l00 with reflux. After the addition of l20 parts of ethanol the reaction mixture is allowed to cool and the product, having settled out, is filtered off, washed with ethanol and water and dried.

IO parts of the dye base thus formed are dissolved in 50 parts of 100% sulphuric acid at l-2(). parts of oleum are dropped in and the mixture stirred until a sample is completely soluble in water. It is run onto ice and the precipitate is filtered off with suction and introduced again into 200 parts of water. The suspension is neutralized, the dye salted out, filtered off with suction. washed, dried and ground. It is obtained as a dark powder which gives dyeings of greenish blue shade on wool and synthetic polyamide fibres which are fast to light and wet treatments.

The same dye can be obtained by reacting l l.] parts of l-amino-2-bromo-4-(3,5',5-trimethylcyclohexylaminol-anthraquinone 50 parts of 2-(2'-methoxyethoxy)-ethanol, 2 parts of anhydrous sodium carbonate and 5 parts of 4-methyl-l-mercaptobenzene at which the product is precipitated with 40 parts of ethanol. filtered off with suction, washed with ethanol and water and dried. It is sulphonated as described in the foregoing.

The following Table 3 details further dyes of formula I NII II CH CH3 (XXVII) which give dyeings of greenish blue to reddish blue shade on wool and synthetic polyamide fibres and are characterized in the Table by the meanings of the sub- 8U-85 until no further starting material is present. on 20 stituents R and R Table 3 Example R R R R R 29 Sulpho-3-methylphenyl H H H H 30 sulpho-4-chlorophenyl H H H H 3] sulpho-4-methoxyphenyl H H H H 32 sulpho-2,5-dimethylphenyl H H H H 33 sulphoQ-methoxyphenyl H H H H 34 sulpho-Z-methoxy-S-methylphenyl H H H H 35 sulphophenyl OH H H OH 36 do. OH H H NH 37 sulpho-4-methylphenyl NH H H OH 38 do. NH, H H NH, 39 sulph-Lacetylaminophenyl H CI H H 40 sulpho-4-propionylaminophenyl H H H H 4! sulpho4-bromophenyl H SO ,H H H 42 sulph-4-n-bulylphenyl H SO,H H H 43 do. H H H H 44 sulpho-4-isopropylphenyl H H H H 45 sulpho-4-ethylphenyl H H H H 46 sulpho-4-tert.amylphenyl H H H H 47 sulpho-4-ethoxycarbonylamino H H H H phenyl 48 4-methylphenyl H SO,H H H 49 4-rnethoxyphenyl H SO,H H H 50 Zsulphaloethyl H H H H 51 2-sulphalopropyl-l H H H H 52 I -sulphalopropyl-2 H H H H 53 I -sulphalobutyl2 H H H H 54 4-sulphalobutyl-2 H H H H 55 3-sulphalo-2-hydroxypropyll H H H H 56 do OH H H OH 57 2-sulphato-propyll NH H H NH 58 2-sulphalo-ethyl NH, H H OH 59 do. H (l H H 60 do. H H Cl H 61 4-( sulphophenyl)-4-methyl- H H H H pentyl2 62 do. OH H H OH 63 do. H SO 1"! H H 64 A-(sulphophenyl)-butyl-2 H H H H 65 fi-(sulphophenyl)-2-methyl- H H H H hexyl-4 66 do. H SO H H H 67 do. H H SO H H 68 do. OH H H OH 69 do. NH; H H NH 70 4-( sulphophenyl l-butylJ. NH, H H OH 7| do. H Cl H H 72 sulphobenzyl H Cl H H 73 do. OH H H OH 74 do. NH H H NH, 75 Z-(sulphophenylethyll-cyclohexyl H H H H 76 2-( sulpho-4-methylbenzyl H H H H cyclohexyl 77 2-(sulpho-ZA'-dimethylbenzyl]- H H H H cyclohexyl 78 2-( 3 'sulpho-2 4',6'-trime- H H H H thylbenzyh-cyclohexyl 79 2-l sulpho-4'methoxybenzyl H H H H cyclohexyl 80 2 (sulpho-4'-ethoxybenzyl)- H H H H cyclohexyl 8| 2-(sulpho-2',4'-dimethoxyben- H H H H zyl l-cyclohexyl Table 3 Continued Example R 82 2-( sulphobcnzyl i-4-melhyl-cyclohexyl SO -.H

SO H

SO H

HHHHHHHH HHHHHHHH 'l henyl 3-ucetylaminophenyl 2.4-dimelhylphenyl 2,4,6-lrimelh nfyl y phenyl 89 J-chlorophenyl 90 d-methoxyphen 94 ylphe 95 2-methoxy-5-meth wool and synthetic polyamide fibres and are distinguished by the meanings of alkylene, R and R to {11 R19 CH; CH; (XXVIII) TABLE 4 Alkylene The following Table 4 gives details of further dyes of 20 which give greenish blue to reddish blue dyeings on formula HmH HHHHoNoHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH H H m 1 m HHHHHHHHHHHH HHHHHHHHCHHHHHHHHHHHHHHHHHH HHHHHHHHHHHHHHH H m m H HHH H.

l 0 0 I 0 0 HHHCHHHH H HHHHHHHHH H HHHHHHHHHHHHHHHH H HHHHHHHHH HH phenyl.

29 30 Examples 14 and 2 S 01H (5 NHCHz-CH2C 0NH CH: (L NH H2 C Ha CH:

Example 15 C H: CH3 S 011-! 2% NH H OH; CH;

Examples 16 and 25..- CH;

(2; NH H C CHu H0: S CH3 1 O NH H CH3 CH3 Examples 17 and 18 S 011-] (I? NHCHCH2-CH NH H CH3 CH3 Example 19 NH- H Example 23 HO O I]IHC:H4OS 03H CH3 I l H O NH H CH; CH

Example 24 S 0 H HO o NH-om CH3 t H O NH- H CH3 CH3 Example 26 H 0 NH;

OC Hg-CHCHOS 0 H t C H: O

NH- H CH; CH;

Example 27 NH H son:

CH: i Y O NH H CH3 CH;

Example 28 1 NH; S 03H CH: 1 Y 0 NH- H CH: CH:

Having thus disclosed the invention, what we claim is:

l. A compound of the formula ygcn.

w az-szil so I on, H; 0 II 6. The anthraquinone compound according to claim 4 of the formula C") NH2 l o NII 11 crn 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 wherein X is oxygen.
 3. A compound according to claim 2 wherein each R1 is hydrogen.
 4. A compound according to claim 3 wherein R6 is -CH2-CH2-, -CH2-CH2-CH2-,
 5. A compound according to claim 1 wherein R6 is -CH2-CH2-, -CH2-CH2-CH2-,
 6. The anthraquinone compound according to claim 4 of the formula 